- SILYL-NITROGEN COMPOUNDS I. REACTIONS OF DILITHIUM BIS(TRIMETHYLSILYLL)HYDRAZINE WITH GROUP IV HALIDES
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Dilithium 1,2-bis(trimethylsilyl)hydrazine (1) reacts with CCl4, Me3SiCCl3 and CBr4 to form predominantly bis(trimethylsilyl)aminocarbonimidic dichloride, bis(trimethylsilyl)aminoisocyanide and bis(trimethylsilyl)diazene, whereas similar reactions with HCCl3, HCI3, H2CCl2, H2CI2, C2H4Cl2 or C2H2Cl4 lead to increasing amounts of bis(trimethylsilyl)hydrazine.In addition to the hydrazone, (Me3Si)2N-N=CH(Cl), the reaction of 1 with CHCl3 forms a small amount of triazasilacyclopentane,.............. .In contrast, Me2SnCl2 reacts with 1 to give tetraazadistannacyclohexane (Me2Sn(NSiMe3)2)2, whereas SnCl4, SnCl2 and PbCl2 act mainly as oxidants and Me2SiCl2 forms polymers.Another product of the reaction of 1 with SnCl2 or PbCl2 is LiN(SiMe3)2 originating perhaps from LiNH(SiMe3) or (LiNN(SiMe3)2)2.
- Vasisht, Sham Kumar,Sood, Mohini,Sood, Nirupma,Singh, Gursharan
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- Silyl-nitrogen compounds, III: Synthesis and characterisation of pentasila-phospha and pentasila-arsa pentazenes
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Heteroatom incorporated pentazenes, pentakis(trimethylsisyl)-3-phospha-2-pentazene (Me3Si)2N-N-(SiMe3)2 and pentakis(trimethylsilyl)-3-arsa-2-pentazene (Me3Si)2N-N(SiMe3)-As=N-N-(SiMe3)2, have been isolated by the reaction of -dichlorophosphine (Me3Si)2N-N(SiMe3)-PCl2, with dilithium-bis(trimethylsilyl)hydrazine Li(SiMe3)N-N(SiMe3)Li and of dichloroarsine (SiMe3)2N-N(SiMe3)-AsCl2 with Li2N2(SiMe3)2, respectively.Both the compounds are reactive solids.The former thermolises slowly at 120 deg C (τ1/2=25 h) whereas the latter decomposes rapidly at 100 deg C and is sensitive to light.Phosphapentazene reacts with methanol both with addition at -P=N- as well as desilylation, wheres, arsapentazene undergoes cleavage reaction.Key words: pentasila-phospha-pentazene, pentasila-arsa-pentazene, synthesis, characterisaeion, reactivity.
- Vasisht, S. K.,Kaur, Tripat P.,Usha, K.,Kaushal, Jyotsna,Bandhu, Kavita
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p. 189 - 196
(2007/10/03)
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- SILYL-NITROGEN COMPOUNDS, II: SYNTHESIS AND CHARACTERISATION OF TETRASILA-PHOSPHA AND TETRASILA-ARSA TETRAZENES
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Lithylated bis(trimethylsilyl)hydrazines, Li2N2(SiMe3)2 and LiHN2(SiMe3)2 react with (Me3Si)2NECl2 (E = P or As) to form hetero atom incorporated tetrazenes, 1,3,4,4-tetrakis(trimethylsilyl)-2-phospha-1-tetrazene (Me3Si)2N-N(SiMe3)-P=NSiMe3 and 1,1,4,4-tetrakis(trimethylsilyl)-2-arsa-2-tetrazene (Me3Si)2N-N=As-N(siMe3)2.The former thermolyses primarily into trisila-phosphatriazene (Me3Si)2N-P=NSiMe3 and tetrasilahydrazine (Me3Si)4N2, whereas, the latter forms tris(trimethylsilyl)hydrazine (Me3Si)3N2H.Phosphatetrazene interacts with CH3OH in an oxidative addition reaction to form -(trimethylsilylimino)-(methoxy)-phosphorane, Me3Si)2N-N(SiMe3)-PH(OCH3)(=NSiMe3), whereas, arsatetrazene undergoes cleavage reaction to yield (Me3Si)3N2H.
- Vasisht, S. K.,Sood, M.,Verma, P. K.,Kaur, T.,Usha, K.
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p. 349 - 355
(2007/10/02)
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- Partially Substituted Tetrazenes (Me3E)nN4H4-n (E = Si, Ge, Sn): Preparation, Characterization, and Thermolysis
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Partially substituted tetrazenes (Me3E)nN4H4-n (E = Si, Ge, Sn) can be prepared by protolysis of higher substituted tetrazenes (Me3E)oN4H4-o (o > n) or by silylation, germylation, or stannylation of lower substituted tetrazenes (Me3E)mN4H4-m (m 140 deg C1/2 = 3/4 h), of (Me3Si)2N-N=N-NH2 to Me3SiN3 and Me3SiNH2 (concentrated solution; τ40 deg C1/2 ca. 1/4 h), and of (Me3Si)HN-N=N-NH(SiMe3) to N2 and (Me3Si)2N-NH2 (dilute solution; τ140 deg C1/2 > 1 h) or to HN3 and (Me3Si)2NH (concentrated solution; τ140 deg C1/2 1 h).
- Wiberg, Nils,Meyers, Rene,Vasisht, Sham Kumar,Bayer, Heiner
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p. 2886 - 2899
(2007/10/02)
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